The research described in this thesis is aimed at demonstrating the synthetic utility of the asymmetric amino-Cope rearrangement and highlight its potential for future application in natural product synthesis. Using the recently developed asymmetric anionic amino-Cope methodology, rearrangement of diasteromerically pure 3-amino-l,5-hexadiene substrates provided the target aldehyde in good yield and with high levels of asymmetric induction (up to 94% e.e.). The aldehyde obtained was used for the successful formation of2,4-disubstituted lactones with no apparent loss of stereochemical integrity. This could lead to a plausible route to biologically significant compounds.